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Electronic Supplementary Information
Nickel-catalyzed cross-coupling of β-carbonyl alkenyl pivalates with
arylzinc chlorides
Wen-Jing Pan† and Zhong-Xia Wang*,†,‡
† CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical
Sciences at Microscale and Department of Chemistry, University of Science and Technology
of China, Hefei, Anhui 230026, P. R. China.
‡ Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin
300072, P. R. China.
Contents
1. Stability study of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3-en-2-one
and monitoring of reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl
3
(1) 1H NMR spectra of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-
3- en-2-one
3
(2) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-
MeC6H4ZnCl
5
(i) GC of the pure samples for comparison 5
(ii) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-
MeC6H4ZnCl
6
(iii) GC-MS of the reaction mixture (reaction time: 1 h) 8
2. Copies of NMR spectra of the β-carbonyl alkenyl pivalates 13
(1) (E)-4-oxopent-2-en-2-yl pivalate (1a) 13
(2) (E)-4-oxo-4-phenylbut-2-en-2-yl pivalate (1b) 14
(3) 3-oxocyclopent-1-en-1-yl pivalate (1c) 15
(4) ethyl (E)-3-(pivaloyloxy)but-2-enoate (1d) 16
(5) (E)-4-(dimethylamino)-4-oxobut-2-en-2-yl pivalate (1g) 17
3. Copies of NMR spectra of the cross-coupling products 18
(1) (E)-4-(p-tolyl)pent-3-en-2-one 18
(2) (E)-4-(4-(dimethylamino)phenyl)pent-3-en-2-one 19
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018
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(3) (E)-4-(4-methoxyphenyl)pent-3-en-2-one 20
(4) (E)-4-(4-(trifluoromethyl)phenyl)pent-3-en-2-one 21
(5) (E)-4-(o-tolyl) pent-3-en-2-one 22
(6) (Z)-4-(o-tolyl) pent-3-en-2-one 23
(7) (E)-4-(thiophen-2-yl)pent-3-en-2-one 24
(8) (E)-3-(4-(dimethylamino)phenyl)-1-phenylbut-2-en-1-one 25
(9) (E)-(4-methoxyphenyl)-1-phenylbut-2-en-1-one 26
(10) (E)-1-phenyl-3-(p-tolyl)but-2-en-1-one 27
(11) (E)-1-phenyl-3-(4-(trifluoromethyl)phenyl)but-2-en-1-one 28
(12) 3-(4-(dimethylamino)phenyl)cyclopent-2-en-1-one 29
(13) 3-(4-methoxyphenyl)cyclopent-2-en-1-one 30
(14) 3-(p-tolyl)cyclopent-2-en-1-one 31
(15) 3-(4-(trifluoromethyl)phenyl)cyclopent-2-en-1-one 32
(16) 3-(furan-2-yl)cyclopent-2-en-1-one 33
(17) 3-(thiophen-2-yl)cyclopent-2-en-1-one 34
(18) ethyl (E)-3-(4-(dimethylamino)phenyl)but-2-enoate 35
(19) ethyl (E)-(4-methoxyphenyl)but-2-enoate 36
(20) ethyl (E)-3-(p-tolyl)but-2-enoate 37
(21) ethyl (E)-3-(4-(trifluoromethyl)phenyl)but-2-enoate 38
(22) ethyl (E)-3-(o-tolyl) but-2-enoate 39
(23) ethyl-(E)-3-(furan-2-yl)but-2-enoate 40
(24) ethyl-(E)-3-(thiophen-2-yl)but-2-enoate 41
(25) ethyl 4'-methoxy-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 42
(26) ethyl 4'-methyl-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 43
(27) ethyl 4'-(dimethylamino)-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate 44
(28) 4-(4-(dimethylamino)phenyl)-2H-chromen-2-one 45
(29) 4-(4-methoxyphenyl)-2H-chromen-2-one 46
(30) 4-(p-tolyl)-2H-chromen-2-one 47
(31) 4-(4-(trifluoromethyl)phenyl)-2H-chromen-2-one 48
(32) 4-(furan-2-yl)-2H-chromen-2-one 49
(33) 4-(thiophen-2-yl)-2H-chromen-2-one 50
(34) 3-(4-(dimethylamino)phenyl)-N,N-dimethylbut-2-enamide 51
(35) 3-(4-methoxyphenyl)-N,N-dimethylbut-2-enamide 52
(36) N,N-dimethyl-3-(p-tolyl)but-2-enamide 53
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1. Stability study of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3- en-
2-one and monitoring of reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl
NMR spectra were recorded by a Bruker av 400 instrument at room temperature. The GC were
recorded by Agilent Technologies 7820A GC System, and GC-MS was determined by Thermo
Trace-1300 ISQ-Mass spectrometer.
(1) 1H NMR spectra of (E)-4-oxopent-2-en-2-yl pivalate, and (Z)- and (E)-4-o-tolylpent-3-en-
2-one
Figure S1. (a) 1H NMR spectrum of (E)-4-oxopent-2-en-2-yl pivalate in CDCl3; (b) 1H NMR
spectrum of the same sample recorded after 42 h.
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Figure S2. (a) 1H NMR spectrum of (Z)-4-o-tolylpent-3-en-2-one in CDCl3; (b) 1H NMR spectrum of the same sample recorded after 37 h.
Figure S3. (a) 1H NMR spectrum of (E)-4-o-tolylpent-3-en-2-one in CDCl3; (b) 1H NMR spectrum of the same sample recorded after 37 h.
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(2) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl
(i) GC of the pure samples for comparison
Figure S4. GC of (E)-4-oxopent-2-en-2-yl pivalate
Figure S5. GC of (Z)-4-o-tolylpent-3-en-2-one
dode
cane
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Figure S6. GC of (E)-4-o-tolylpent-3-en-2-one
(ii) GC monitoring of the reaction of (E)-4-oxopent-2-en-2-yl pivalate with o-MeC6H4ZnCl
Figure S7. GC monitoring of the reaction (1 h; Z:E = 1:1.91)
dode
cane
Z-i
som
er
E-i
som
er
2,2'
-dim
ethy
lbip
heny
l
NM
P
E-4
-oxo
pent
-2-e
n-2-
yl p
ival
ate
impu
rity
7
Figure S8. GC monitoring of the reaction (3 h; Z:E = 1:2.28)
Figure S9. GC monitoring of the reaction (6 h; Z:E = 1:2.17)
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Figure S10. GC monitoring of the reaction (10 h; Z:E = 1:1.90)
(iii) GC-MS of the reaction mixture (reaction time: 1 h)
Figure S11. GC-MS of the reaction mixture (component 1: NMP)
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Figure S12. GC-MS of the reaction mixture (component 2: (E)-4-oxopent-2-en-2-yl pivalate)
Figure S13. GC-MS of the reaction mixture (component 3: impurity)
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Figure S14. GC-MS of the reaction mixture (component 4: (Z)-4-o-tolylpent-3-en-2-one)
Figure S15. GC-MS of the reaction mixture (component 5: (E)-4-o-tolylpent-3-en-2-one)
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Figure S16. GC-MS of the reaction mixture (component 6: 2,2'-dimethylbiphenyl)
Figure S17. GC-MS of the reaction mixture (component 7: impurity)
12
Figure S18. GC-MS of the reaction mixture (component 8: maybe Cy3P=O)
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2. Copies of NMR spectra of the β-carbonyl alkenyl pivalates (1) (E)-4-oxopent-2-en-2-yl pivalate (1a)
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(2) (E)-4-oxo-4-phenylbut-2-en-2-yl pivalate (1b)
- 1 . 0- 0 . 50 . 00 . 51 . 01 . 52 . 02 . 53 . 03 . 54 . 04 . 55 . 05 . 56 . 06 . 57 . 07 . 58 . 08 . 59 . 0
f 1 ( p p m )
9.2
4
3.0
0
0.9
8
2.0
51
.01
1.9
9
1.3
1
2.3
9
6.7
5
7.4
47
.46
7.4
87
.53
7.5
57
.57
7.9
17
.92
7.9
4
1H N M R (CDC l 3)
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(3) 3-oxocyclopent-1-en-1-yl pivalate (1c)
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(4) Ethyl (E)-3-(pivaloyloxy)but-2-enoate (1d)
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(5) (E)-4-(dimethylamino)-4-oxobut-2-en-2-yl pivalate (1g)
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3. NMR spectral copies of the cross-coupling products
(1) (E)-4-(p-tolyl)pent-3-en-2-one
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(2) (E)-4-(4-(dimethylamino)phenyl)pent-3-en-2-one
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(3) (E)-4-(4-methoxyphenyl)pent-3-en-2-one
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(4) (E)-4-(4-(trifluoromethyl)phenyl)pent-3-en-2-one
22
(5) (E)-4-(o-tolyl)pent-3-en-2-one
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(6) (Z)-4-(o-tolyl)pent-3-en-2-one
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(7) (E)-4-(thiophen-2-yl)pent-3-en-2-one
25
(8) (E)-3-(4-(dimethylamino)phenyl)-1-phenylbut-2-en-1-one
26
(9) (E)-(4-methoxyphenyl)-1-phenylbut-2-en-1-one
27
(10) (E)-1-phenyl-3-(p-tolyl)but-2-en-1-one
28
(11) (E)-1-phenyl-3-(4-(trifluoromethyl)phenyl)but-2-en-1-one
29
(12) 3-(4-(dimethylamino)phenyl)cyclopent-2-en-1-one
30
(13) 3-(4-methoxyphenyl)cyclopent-2-en-1-one
31
(14) 3-(p-tolyl)cyclopent-2-en-1-one
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(15) 3-(4-(trifluoromethyl)phenyl)cyclopent-2-en-1-one
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(16) 3-(furan-2-yl)cyclopent-2-en-1-one
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(17) 3-(thiophen-2-yl)cyclopent-2-en-1-one
35
(18) ethyl (E)-3-(4-(dimethylamino)phenyl)but-2-enoate
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(19) ethyl (E)-(4-methoxyphenyl)but-2-enoate
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(20) ethyl (E)-3-(p-tolyl)but-2-enoate
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(21) ethyl-(E)-3-(4-(trifluoromethyl)phenyl)but-2-enoate
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(22) ethyl (E)-3-(o-tolyl) but-2-enoate
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(23) ethyl-(E)-3-(furan-2-yl)but-2-enoate
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(24) ethyl-(E)-3-(thiophen-2-yl)but-2-enoate
42
(25) ethyl 4'-methoxy-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate
43
(26) ethyl 4'-methyl-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate
44
(27) ethyl 4'-(dimethylamino)-3,4,5,6-tetrahydro-[1,1'-biphenyl]-2-carboxylate
45
(28) 4-(4-(dimethylamino)phenyl)-2H-chromen-2-one
46
(29) 4-(4-methoxyphenyl)-2H-chromen-2-one
47
(30) 4-(p-tolyl)-2H-chromen-2-one
48
(31) 4-(4-(trifluoromethyl)phenyl)-2H-chromen-2-one
49
(32) 4-(furan-2-yl)-2H-chromen-2-one
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(33) 4-(thiophen-2-yl)-2H-chromen-2-one
51
(34) 3-(4-(dimethylamino)phenyl)-N,N-dimethylbut-2-enamide
52
(35) 3-(4-methoxyphenyl)-N,N-dimethylbut-2-enamide
53
(36) N,N-dimethyl-3-(p-tolyl)but-2-enamide